CN101501128A - Propylene resin composition for packaging material - Google Patents

Propylene resin composition for packaging material Download PDF

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Publication number
CN101501128A
CN101501128A CNA2007800295152A CN200780029515A CN101501128A CN 101501128 A CN101501128 A CN 101501128A CN A2007800295152 A CNA2007800295152 A CN A2007800295152A CN 200780029515 A CN200780029515 A CN 200780029515A CN 101501128 A CN101501128 A CN 101501128A
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Prior art keywords
propylene
resin composition
ethene
film
packaging material
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CN101501128B (en
Inventor
板仓启太
木村笃太郎
河田充生
桥诘聪
樋口匡史
船谷宗人
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Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
Prime Polymer Co Ltd
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Mitsui Chemical Industry Co Ltd
Prime Polymer Co Ltd
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Priority claimed from JP2007169207A external-priority patent/JP5342115B2/en
Application filed by Mitsui Chemical Industry Co Ltd, Prime Polymer Co Ltd filed Critical Mitsui Chemical Industry Co Ltd
Priority claimed from PCT/JP2007/065362 external-priority patent/WO2008018409A1/en
Publication of CN101501128A publication Critical patent/CN101501128A/en
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Publication of CN101501128B publication Critical patent/CN101501128B/en
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  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Wrappers (AREA)

Abstract

A propylene resin composition for packaging materials which has an excellent balance among high transparency, rigidity, low-temperature impact resistance, and blocking resistance; a retort film, protective film, film for medical containers/packages, and freshness-maintaining film which are obtained from the composition; and sheets of these. The propylene resin composition for packaging materials is characterized by comprising a propylene polymer (A) satisfying a specific requirement and a propylene/ethylene copolymer (B) satisfying a specific requirement or by having values of Dinsol and Dsol which satisfy a specific requirement.

Description

Propylene resin composition for packaging material
Technical field
The present invention relates to have the propylene resin composition for packaging material of special properties.Further specifically, the propylene resin composition for packaging material that relates to rigidity, the transparency, shock-resistance, resistance to blocking excellence.
Background technology
Propenes resin composition is used to various fields such as sundry goods, kitchen tackle, film for packaging, tame electrical article, mechanical part, electric component, trolley part.Particularly, the various Propenes resin compositions that require function have been proposed to adapt in the film for packaging field.But, many film fields that continuous appearance only uses existing Propenes resin composition not tackle.Specifically can enumerate boiling film, protective membrane, medical wrapping material or fresh-keeping packaging material.
In recent years, cooking food begins rapidly to popularize to the business field from general family, and demand is the wrapping material of the more substantial cooking food of utilization in the general family of packing ratio once.Cooking food since usually long-time normal temperature preserve or cryopreservation, so wrapping body breaks or wrapping body from the heat-sealing portion breakage of wrapping body, the wrapping material film that the desired content thing does not leak with high heat-sealing strength and low-temperature impact-resistant intensity.In addition, above-mentioned wrapping material are being used for film under the situation of cooking food, after filling content and the sealing, under the high temperature about 100～140 ℃, are using autoclave to carry out cooking disinfection and handle.Therefore, from the qualitative control aspect of food, above-mentioned wrapping material also require to be the thermotolerance that can tolerate the such maintenance heat-sealing portion of this processing and the film of heat seal strength with film.
The wrapping material film that uses in this cooking food is extensive use of the blend film (blend film), polypropylene block copolymer film of polypropylene and ethene-alpha-olefin copolymer rubber or the film that is obtained by the blending resin composition of this polypropylene block copolymer and ethene-alpha-olefin copolymer rubber.But it is excellent on the balance of the salient features of film as wrapping material at thermotolerance, low-temperature impact-resistant intensity, resistance to blocking and heat sealability etc. to be difficult to these films, particularly has very big problem on the balance of low-temperature impact-resistant intensity and heat sealability.For example, handle post heat-seal intensity and reduce, in patent documentation 1, proposed propylene-'alpha '-olefin block copolymers that hot sealing layer uses the elastomeric blocks by the polypropylene block of 95～70 weight % and 5～30 weight % to constitute in order to prevent boiling as far as possible.But, concrete disclosed film is in this communique, by using ziegler-natta catalyzer class, obtains containing the propylene-ethylene block copolymer of the widespread elastomeric blocks of composition of 30～70 moles of % of propylene content, by the film that this multipolymer forms, its low-temperature impact-resistant undercapacity.
On the other hand, in patent documentation 2, the crystalline p p sheet and the film that are obtained by the propylene-based block copolymer that uses the manufacturing of metallocene catalyst class have been proposed.These sheet materials and film are formed uniform propylene-based block copolymer by elastomeric blocks and are obtained, so, realized the raising of shock-resistance.[η] that disclose in this communique in fact as the part that dissolves in n-decane of elastomeric blocks is the acronal more than the 2.5dl/g.Disclosed film in this communique, its low temperature shock-resistance improves, but the transparent deterioration of film.In addition,, wherein wrapping material are also required decrement with film because the importance of environmental problem improves in recent years, so, even demand also can keep shock-resistance, have a high inflexible film simultaneously for film.
As the developing trend of boiling wrapping material, require to have the transparency that to have an X-rayed the packed article degree sometimes.As the advantage of high transparentization, can enumerate can corresponding microwave oven, can the identification content, the metal on production line finds out and becomes easy etc.In order to improve the transparency, in patent documentation 3, the resin combination by ethene-propylene-butene-1 copolymer formation of propylene class homopolymer that uses metallocene catalyst to make and manufacturing in the presence of metallocene catalyst has been proposed.But the film of concrete record in this communique though the transparency is excellent, for as the boiling desired low temperature shock-resistance of film, rigidity, also exists room for improvement.
In addition, in patent documentation 4, the resin combination that is made of the propylene-ethylene atactic copolymer that uses metallocene catalyst to make and ethene-alpha-olefin copolymer has been proposed.But, the film of particular instantiation in this communique, though the transparency, shock-resistance is excellent, the thermotolerance deficiency that high temperature steaming is handled.
On the other hand, the protective membrane that is made of Propenes resin composition in the past for when the domestic trade of automobile and the outlet, prevents the purpose of surface tear and uses.The characteristic that requires as protective membrane, the easiness of the cementability of appropriateness, strip operation when attaching this film in the metallic surface, the intensity of tearing etc. are necessary.For example, in patent documentation 5, disclose the protective membrane that constitutes by the propylene-based block copolymer that uses the manufacturing of ziegler-natta catalyzer, put down in writing the protection that this film is suitable for the metallic surface.But, the propylene-based block copolymer of concrete record in this communique because the molecular weight distribution of rubber constituent is wide, so low molecular weight rubber oozes out sometimes, bounding force take place through the time variation.In addition, in recent years with the background of expanding as in liquid-crystal display market, the surface protection film of the various optical sheets that use in indicating meter at liquid crystal increases.At optical sheet with in the protective membrane, for suppress bounding force through the time change and make the visual inspection facilitation, require flake few and have a high transparent.
In addition, medical container materials such as infusion preparation container change to plastic material from frit.As infusion preparation container material, used poly situation many, but in recent years, the trend that exists the polypropylene of the balance excellence of flexibility, moisture resistance, water-repellancy, resistance to chemical reagents etc. to increase in the past.Particularly because of the sterilization that abroad requires under 121 ℃, so if from stable on heating viewpoint, polypropylene is also favourable than polyethylene.But than polyethylene, polyacrylic low temperature poor impact resistance is so at cold district, when mistake falls the infusion preparation container etc., might cause container generation broken bag.As the method for improving polyacrylic low temperature shock-resistance, can consider to use the method for propylene-based block copolymer, but in existing propylene-based block copolymer, have the problem of the transparency and shock-resistance, stable on heating balanced differences.
In addition, use in the wrapping material the fresh-keeping of vegetables and fruits such as vegetables and fruit, demand is to the high gas permeation degree of oxygen, carbonic acid gas, ethene etc.For example, in patent documentation 6, the film that is made of the Propenes resin composition that contains the improved propylene-alpha-olefin copolymer of gas-premeable has been proposed.But though this film has good gas permeation degree, the rigidity of film is low, have problems on practicality.
In addition, in patent documentation 7, the film that is made of the resin combination that contains polypropylene and ethene-1-octene random copolymers has been proposed.If according to this communique, the rigidity of gas-premeable, film is all good, but needs the operation of mixing polypropylene and ethene-1-octene, has the big problem of cost height and energy consumption.
Patent documentation 1: the Japanese Patent spy opens communique 2000-No. 255012
Patent documentation 2: the Japanese Patent spy opens communique 2006-No. 152068
Patent documentation 3: the Japanese Patent spy opens communique 2001-No. 172402
Patent documentation 4: the Japanese Patent spy opens communique 2004-No. 3597711
Patent documentation 5: the Japanese Patent spy opens communique 2000-No. 168006
Patent documentation 6: the Japanese Patent spy opens communique 2001-No. 106802
Patent documentation 7: the Japanese Patent spy opens communique 2006-No. 299229
Summary of the invention
In order to solve problem as described above; the objective of the invention is to; a kind of propylene resin composition for packaging material is provided, and this propylene resin composition for packaging material is fit to obtain the boiling of balance excellence of high transparent, rigidity, low temperature shock-resistance, resistance to blocking with film, protective membrane.The present invention also aims to, by using this composition, the boiling of balance excellence that high transparent, rigidity, low temperature shock-resistance, resistance to blocking be provided with film, protective membrane, medical container film for packaging and Freshkeeping Packaging with film and their sheet material.
Promptly, the present invention is a kind of propylene resin composition for packaging material and the sheet material or the film that are obtained by said composition, this propylene resin composition for packaging material is characterised in that: comprise the acronal (A) of the following important document of satisfying of 60～90 weight % (a1)～(a2) and the propylene-ethylene copolymer that satisfies following important document (b1)～(b4) (B) of 40～10 weight % (wherein, (A)+(B)=100 weight %).
Acronal (A):
(a1) melt flow rate (MFR) (MFR, ASTM D1238,230 ℃, load 2.16kg) is 0.1～40 (g/10min);
(a2) fusing point of measuring with differential scanning type calorimeter (DSC) (Tm) is 145 ℃～170 ℃.
Propylene-ethylene copolymer (B):
(b1) content from the structural unit of ethene is more than the 15mol% and less than 45mol%;
(b2) be 1.8dl/g～3.5dl/g in naphthane solvent, 135 ℃ limiting viscosity [η];
(b3) molecular weight distribution (Mw/Mn) is below 3.5;
(b4) be more than the 95 weight % 23 ℃ of parts that dissolve in n-decane.
In addition, the present invention is a kind of propylene resin composition for packaging material and the sheet material or the film that are obtained by said composition, and this propylene resin composition for packaging material is characterised in that: comprise the following important document of satisfying of 60～90 weight % (a1 ')～(a2 ') at 23 ℃ of part (D that are insoluble to n-decane Insol) and 40～10 weight % satisfy following important document (b1 ')～(b3 ') at 23 ℃ of part (D that dissolve in n-decane Sol), and melt flow rate (MFR) (MFR, ASTMD1238,230 ℃, load 2.16kg) is in the scope of 0.1～20 (g/10min).
Be insoluble to the part (D of n-decane Insol):
(a1 ') is below the 2 weight % from the content of the structural unit of ethene;
The fusing point (Tm) that (a2 ') measures with differential scanning type calorimeter (DSC) is 145 ℃～170 ℃.
Dissolve in the part (D of n-decane Sol):
(b1 ') is more than the 15mol% and less than 45mol% from the content of the structural unit of ethene;
(b2 ') is 1.8dl/g～3.5dl/g in naphthane solvent, 135 ℃ limiting viscosity [η];
(b3 ') molecular weight distribution (Mw/Mn) is below 3.5.
The invention effect
The sheet material or the film that make Propenes resin composition moulding of the present invention and obtain, compare its transparency, low temperature shock-resistance and inflexible balance excellence with sheet material or film that propylene-based block copolymer by the manufacturing of existing use ziegler-natta class catalyzer obtains.
Embodiment
Propylene resin composition for packaging material of the present invention comprises acronal (A) and propylene-ethylene copolymer (B).
Below describe each composition in detail.
(1) acronal (A)
As the acronal (A) of one of composition that forms propylene resin composition for packaging material of the present invention,
(a1) melt flow rate (MFR) (MFR, ASTM D1238,230 ℃, load 2.16kg) the scope of 0.1～40 (g/10min), preferably in the scope of 0.5～20 (g/10min), more preferably in the scope of 1.0～10 (g/10min),
(a2) fusing point of measuring with differential scanning type calorimeter (DSC) (Tm) 145 ℃～170 ℃ scope, preferably 150 ℃～170 ℃ scope, more preferably 155 ℃～170 ℃ scope.
MFR is less than the acronal of 0.1 (g/10min), mixes with propylene-ethylene copolymer (B) and the extrusion moulding of the propylene resin composition for packaging material that obtains might worsen.If greater than 40 (g/10min), then there is the trend of the low-temperature impact deterioration of the sheet material obtain or film.
Fusing point is lower than 145 ℃ acronal, sheet material that obtains or film heat resistance deterioration, and film may soften when boiling is handled, and particularly is not suitable as the high temperature steaming film sometimes.In addition, the differences in viscosity of the film that obtains sometimes can occur wrinklingly when being attached to product surface, the worry that is not suitable as protective membrane is also arranged.
Acronal of the present invention (A) is an alfon, or propylene and on a small quantity, the multipolymer of following other alpha-olefin of 2 weight % for example.As alpha-olefin, preferably use ethene, 1-butylene, 1-hexene, 1-octene.
The molecular weight distribution (Mw/Mn) of acronal of the present invention (A) is preferably below 3.5, more preferably below 3.0, more preferably below 2.5.Propylene resin composition for packaging material by comprising the acronal (A) with this molecular weight distribution can access more excellent sheet material or films such as the transparency, shock-resistance, resistance to blocking.
Acronal of the present invention (A) is preferably made in the presence of metallocene catalyst.As the metallocene catalyst that in the manufacturing of acronal (A), uses, as described later, can use comprise metallocene compound and be selected from organometallic compound, Organoaluminoxy compound and can with the compound more than at least a kind in the right compound of metallocene compound reacting forming ion and the metallocene catalyst of granular carrier as required, suitable use is by the applicant's disclosed bridging property metallocene compound in above-mentioned communique (WO01/27124) or 11-No. 315109 communiques of Japanese patent laid-open.
(2) propylene-ethylene copolymer (B)
As the propylene-ethylene copolymer (B) of other composition that forms propylene resin composition for packaging material of the present invention,
(b1) from the content of the structural unit of ethene more than 15mol% and less than the scope of 45mol%,
(b2) the naphthane solvent, 135 ℃ limiting viscosity [η] the scope of 1.8dl/g～3.5dl/g, preferably in the scope of 1.9dl/g～3.0dl/g, more preferably in the scope of 2.0dl/g～2.5dl/g,
(b3) molecular weight distribution (Mw/Mn) the scope below 3.5, preferably in the scope below 3.0, more preferably in the scope below 2.5,
(b4) 23 ℃ of parts that dissolve in n-decane in the scope more than the 95 weight %, preferably in the scope more than the 98 weight %, the more preferably scope more than 99 weight %.
From the content of the structural unit of the ethene multipolymer less than 15mol%, the sheet material that obtains or the shock-resistance of film might worsen.Content is the above multipolymer of 45mol%, and the sheet material that existence obtains or the transparent downward trend of film are so be not suitable as transparent boiling film sometimes.
Limiting viscosity [η] is less than the multipolymer of 1.8dl/g, and the sheet material that obtains or the shock-resistance of film might descend.On the other hand, limiting viscosity [η] is greater than the multipolymer of 3.5dl/g, and the transparency might worsen, so be not suitable as transparent boiling film.In addition, if limiting viscosity [η] greater than 3.5dl/g, produces flake easily on sheet material that obtains or film, so be not suitable as boiling film and protective membrane sometimes.
Molecular weight distribution (Mw/Mn) is greater than 3.5 multipolymer; because low molecular weight compositions increases; so the sheet material that obtains sometimes or the shock-resistance of film and tear strength descend, and because the possibility that exists low-molecular weight polymer to emit, so be not suitable as boiling film and protective membrane sometimes.
At 23 ℃ of multipolymers that dissolve in the part of n-decane less than 95 weight %, the composition of propylene-ethylene copolymer distributes wide, and the sheet material that obtains or the rigidity of film, shock-resistance descend, so be not suitable as boiling film and protective membrane sometimes.
Propylene-ethylene copolymer of the present invention (B) is preferably made in the presence of metallocene catalyst.As the metallocene catalyst that in the manufacturing of propylene-ethylene copolymer (B), uses, as described later, can use comprise metallocene compound and be selected from organometallic compound, Organoaluminoxy compound and can with the compound more than at least a kind in the right compound of metallocene compound reacting forming ion and the metallocene catalyst of granular carrier as required, suitable use is by the applicant's disclosed bridging property metallocene compound in above-mentioned communique (WO01/27124) or 11-No. 315109 communiques of Japanese patent laid-open.
Propylene resin composition for packaging material of the present invention also has first form and second form, in each form, (a1) melt flow rate (MFR) of aforesaid propylene base polymer (A), (b1) of aforesaid propylene-ethylene copolymer (B) are as described below from the content of the structural unit of ethene.
[first form]
First form of propylene resin composition for packaging material of the present invention is characterised in that, (b1) of aforesaid propylene-ethylene copolymer (B) from the content of the structural unit of ethene the scope of 15mol%～25mol%, preferably in the scope of 17mol%～25mol%, more preferably in the scope of 18～23mol%.
If (b1) of aforesaid propylene-ethylene copolymer (B) in above-mentioned scope, then can bring into play the effect of the balance excellence of the transparency of the sheet material that obtains or film and resistance to blocking from the content of the structural unit of ethene.
[second form]
Second form of propylene resin composition for packaging material of the present invention is characterised in that, (b1) of aforesaid propylene-ethylene copolymer (B) from the content of the structural unit of ethene greater than 25mol%, less than the scope of 45mol%, preferably in the scope of 27mol%～40mol%, more preferably in the scope of 30～35mol%.If (b1) of aforesaid propylene-ethylene copolymer (B) in above-mentioned scope, then can bring into play the effect of the balance excellence of the shock-resistance of the sheet material that obtains or film and the transparency from the content of the structural unit of ethene.
(3) Propenes resin composition
Propylene resin composition for packaging material of the present invention is following propylene resin composition for packaging material (below be also referred to as " composition C1 "), in (A) and the 100 weight % of total (B), contain 60～90 weight %, preferred 70～85 weight %, more preferably the aforesaid propylene base polymer (A) of 80～85 weight % and 40～10 weight %, preferred 30～15 weight %, the more preferably aforesaid propylene-ethylene copolymer of the scope of 20～15 weight % (B).
The amount of acronal (A) is less than the composition of 60 weight %, and the sheet material that existence obtains or the rigidity downward trend of film are so be not suitable as the boiling film sometimes.On the other hand, greater than the composition of 90 weight %, the sheet material that existence obtains or the shock-resistance downward trend of film are so be not suitable as the boiling film sometimes.
Propylene resin composition for packaging material of the present invention, preferred usually the scope of melt flow rate (MFR) (MFR, ASTM D1238,230 ℃, load 2.16kg) at 0.1～40g/10min.
In addition, propylene resin composition for packaging material of the present invention is following propylene resin composition for packaging material (below be also referred to as " composition C2 "), said composition is characterised in that, comprise satisfy following important document (a1 ')～(a2 ') at 23 ℃ of part (D that are insoluble to n-decane Insol) 60～90 weight %, be preferably 70～85 weight %, more preferably 77～83 weight % and satisfy following important document (b1 ')～(b3 ') at 23 ℃ of part (D that dissolve in n-decane Sol) 40～10 weight %, be preferably 30～15 weight %, 23～17 weight % more preferably, and melt flow rate (MFR) (MFR, ASTM D1238,230 ℃, load 2.16kg) scope at 0.1～20 (g/10min).
Be insoluble to the part (D of n-decane Insol):
(a1 ') is below the 2 weight % from the content of the structural unit of ethene;
The fusing point (Tm) that (a2 ') measures with differential scanning type calorimeter (DSC) 145 ℃～170 ℃ scope, preferably 150 ℃～170 ℃ scope, more preferably greater than the scope below 155 ℃ and 170 ℃.
Dissolve in the part (D of n-decane Sol):
(b1 ') from the content of the structural unit of ethene more than 15mol% and less than the scope of 45mol%;
(b2 ') the naphthane solvent, 135 ℃ limiting viscosity [η] the scope of 1.8dl/g～3.5dl/g, preferably in the scope of 1.9dl/g～3.0dl/g, more preferably in the scope of 2.0dl/g～2.5dl/g;
(b3 ') molecular weight distribution (Mw/Mn) the scope below 3.5, preferably in the scope below 3.0, more preferably in the scope below 2.5.
Propylene resin composition for packaging material of the present invention also has first form and second form, in each form, and the above-mentioned part (D that dissolves in n-decane Sol) (b1 ') as described below from the content of the structural unit of ethene.
[first form]
First form of propylene resin composition for packaging material of the present invention is characterised in that, the above-mentioned part (D that dissolves in n-decane Sol) (b1 ') from the content of the structural unit of ethene the scope of 15mol%～25mol%, preferably in the scope of 17mol%～25mol%, more preferably in the scope of 18～23mol%.If the above-mentioned part (D that dissolves in n-decane Sol) (b1 ') from the content of the structural unit of ethene in above-mentioned scope, then can bring into play the effect of the balance excellence of the transparency of the sheet material that obtains or film and resistance to blocking.
[second form]
Second form of propylene resin composition for packaging material of the present invention is characterised in that, the above-mentioned part (D that dissolves in n-decane Sol) (b1 ') from the content of the structural unit of ethene greater than 25mol% and less than the scope of 45mol%, preferably in the scope of 27mol%～40mol%, more preferably in the scope of 30～35mol%.If the above-mentioned part (D that dissolves in n-decane Sol) (b1 ') from the content of the structural unit of ethene in above-mentioned scope, then can bring into play the effect of the balance excellence of the shock-resistance of the sheet material that obtains or film and the transparency.
(4) other composition
In propylene resin composition for packaging material of the present invention (comprising above-mentioned composition C1 and composition C2), except that acronal (A) and propylene-ethylene copolymer (B) etc., can also contain other polymkeric substance.Particularly, can contain ethene-alpha-olefin copolymer (D), ethene-propylene copolymer (B '), acronal (I ') etc.
" ethene-alpha-olefin copolymer (D) "
In propylene resin composition for packaging material of the present invention, the sheet material that obtains with further improvement or the functions such as shock-resistance of film are purpose, can add ethene-alpha-olefin copolymer (D).As the alpha-olefin in this ethene-alpha-olefin copolymer (D), can enumerate the alpha-olefin of carbonatoms 4～20, preferred 1-butylene, 1-hexene, 1-octene etc.In addition, the density of ethene-alpha-olefin copolymer (D) is generally 0.850～0.910g/cm 3, be preferably 0.860～0.890g/cm 3
Density is less than 0.850g/cm 3Multipolymer, the sheet material that obtains or the transparency of film or resistance to blocking worsen easily, are not suitable as the boiling film sometimes.On the other hand, density is greater than 0.910g/cm 3The time, the sheet material that obtains or the shock-resistance of film might descend, and exist and to be easy to generate the trend of flake, so be not suitable as the boiling film sometimes.In propylene resin composition for packaging material (100 weight %), the addition of ethene-alpha-olefin copolymer (D) the scope of 0～15 weight %, preferably in the scope of 0～10 weight %, more preferably in the scope of 0～5 weight %.
" ethene-propylene copolymer (B ') "
In propylene resin composition for packaging material of the present invention, the sheet material that obtains with further improvement or the functions such as shock-resistance of film are purpose, can add ethene-propylene copolymer (B '), this ethene-propylene copolymer (B ') have different with aforesaid propylene-ethylene copolymer (B) structural units from ethene content or with the part (D that dissolves in n-decane of composition C2 Sol) the different amount of content of contained structural unit from ethene.
The content from the structural unit of ethene of this ethene-propylene copolymer (B '), preferably the scope of 25～85mol%, more preferably in the scope of 30～70mol%, further preferably in the scope of 30～55mol%.
As ethene-propylene copolymer (B '),, wish in the presence of metallocene catalyst, to make from improving the sheet material that obtains by propylene resin composition for packaging material or the shock-resistance of film, the viewpoint of resistance to blocking.In propylene resin composition for packaging material (100 weight %), the addition of ethene-propylene copolymer (B ') is 0～15 weight %, be preferably 0～10 weight %, 0～5 weight % more preferably.
In addition, ethene-propylene copolymer (B ') can make acronal (A) and propylene-ethylene copolymer (B) in same system during polymerization polymerization add.
" acronal (I ') "
The acronal that adds in propylene resin composition for packaging material of the present invention (I ') is multipolymer, propylene and the ethene of alfon, propylene and ethene and the alpha-olefin of carbonatoms more than 4 and the segmented copolymer of the alpha-olefin of carbonatoms more than 4.Object lesson as above-mentioned alpha-olefin, can enumerate 1-butylene, 2-methyl isophthalic acid-propylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, the 1-hexene, 2-ethyl-1-butylene, 2,3-dimethyl-1-butylene, the 2-Methyl-1-pentene, the 3-Methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butylene, the 1-heptene, methyl isophthalic acid-hexene, dimethyl-1-amylene, ethyl-1-amylene, trimethylammonium-1-butylene, methylethyl-1-butylene, the 1-octene, Methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl group-1-heptene, methylethyl-1-heptene, trimethylammonium-1-amylene, propyl group-1-amylene, diethyl-1-butylene, the 1-nonene, 1-decene, the 1-undecylene, 1-dodecylene etc.Wherein, the alpha-olefin of preferred 1-butylene, 1-amylene, 1-hexene, 1-octene.Also can use more than 2 kinds with ethene copolymerization of propylene and carbonatoms the alpha-olefin more than 4.
The fusing point (Tm) of acronal (I ') is generally 150～170 ℃, is preferably 155～170 ℃.In addition, the melt flow rate (MFR) of acronal (I ') (MFR, ASTM D1238,230 ℃, load 2.16kg) be generally 0.1～10g/10 minute, be preferably 0.5～8g/10 minute, more preferably 1.0～5g/10 minute.
In propylene resin composition for packaging material (100 weight %), the addition of acronal (I ') is 0～50 weight %, be preferably 0～25 weight %, 0～10 weight % more preferably.
In propylene resin composition for packaging material of the present invention, as required, can also in the scope of not damaging the object of the invention, add antioxidant, nucleator, lubricant, fire retardant, antiblocking agent, tinting material, the inorganic or various additives such as organic filler, various synthetic resins that in olefin polymer, add usually.
(5) manufacture method of propylene resin composition for packaging material
Propylene resin composition for packaging material of the present invention can be obtained by various known manufacture method.For example, can enumerate following method: the amount according to above-mentioned record cooperates aforesaid propylene base polymer (A) and the aforesaid propylene-ethylene copolymer (B) that obtains in advance, and cooperate above-mentioned polymkeric substance or various additive as required, for example using, various well known devices such as Henschel mixer, ribbon blender, banbury mixers carry out the blended method; Perhaps mix the back and use single screw extrusion machine or various known mixing rolls such as twin screw extruder, Bradley Bender mixing roll (brabender) or roller, 170～300 ℃, preferably 190～250 ℃ of methods of carrying out melting mixing etc.
In addition, propylene resin composition for packaging material of the present invention can adopt following method, make by making polymerizations such as propylene and ethene.
Making by polymerization under the situation of propylene resin composition for packaging material of the present invention, preferably in the presence of as the metallocene catalyst of catalyzer, implementing following 2 operations ([operation 1] and [operation 2]) continuously, making propylene-based block copolymer.
[operation 1] is in the presence of metallocene catalyst, with the amount of above-mentioned scope, make the propylene homopolymerization or with as required ethylene copolymer, make aforesaid propylene base polymer (A) or at 23 ℃ of part (D that dissolve in n-decane Sol) be the following homopolymer of 0.5 weight % or the operation of multipolymer.
[operation 2] is in the presence of metallocene catalyst, with the amount of above-mentioned scope, makes propylene and ethylene copolymer, makes aforesaid propylene-ethylene copolymer (B) or at 23 ℃ of part (D that are insoluble to n-decane Insol) be the operation of the following multipolymer of 5.0 weight %.
Propylene resin composition for packaging material among the present invention, particularly, the preferred poly-unit that is connected in series with 2 above reactors that uses is made by above-mentioned 2 operations of continuous enforcement ([operation 1] and [operation 2]).
[operation 1] is under 0～100 ℃ of polymerization temperature, polymerization pressure normal pressure～5MPa gauge pressure, makes the propylene homopolymerization or makes propylene and the operation of small amount of ethylene copolymerization.In [operation 1], make the propylene homopolymerization or make propylene and the small amount of ethylene copolymerization, thus the acronal of in [operation 1], making (multipolymer) become in the propylene resin composition for packaging material at 23 ℃ of part (D that are insoluble to n-decane Insol) main component.
[operation 2] is under 0～100 ℃ of polymerization temperature, polymerization pressure normal pressure～5MPa gauge pressure, makes the operation of propylene and ethylene copolymer.In [operation 2], make ethene with respect to the inlet amount of propylene situation more than [operation 1], thus propylene-ethylene copolymer of in [operation 2], making become in the propylene resin composition for packaging material at 23 ℃ of part (D that dissolve in n-decane Sol) main component.
Here, above-mentioned D InsolBe equivalent to acronal contained in the propylene resin composition for packaging material (A) in fact.In addition, above-mentioned D SolBe equivalent to propylene-ethylene copolymer contained in the propylene resin composition for packaging material (B) in fact.
In addition, in propylene resin composition for packaging material, substantially be equivalent to the D of acronal (A) InsolIn, 2 of propylene, 1-inserts binding capacity, 1, and 3-inserts binding capacity for a long time, is equivalent to the D of propylene-ethylene copolymer (B) in fact SolComposition distribute to become wide, rigidity, shock-resistance descend sometimes.So-called 2,1-inserts and 1, and it is the position irregular unit of the propylene in the propylene resin composition for packaging material that 3-inserts, and the part-structure that contains these is with following (i) and (ii) represent.
Structure (i)
Figure A200780029515D00171
Structure (ii)
Figure A200780029515D00172
And, after polymerization in [operation 1] and [operation 2] finishes, as required, carry out known catalyst deactivation treatment process, catalyst residue is removed postprocessing working procedures such as operation, drying process, obtains propylene resin composition for packaging material with powder thus.
(6) metallocene catalyst
In the present invention, acronal (A), propylene-ethylene copolymer (B) or Propenes resin composition are preferably made in the presence of metallocene catalyst.
As the metallocene catalyst that uses in the present invention, can enumerate comprise metallocene compound and be selected from organometallic compound, Organoaluminoxy compound and can with the compound more than at least a kind in the right compound of metallocene compound reacting forming ion and the metallocene catalyst of granular carrier as required, preferably can carry out stereoregularity polymeric metallocene catalysts such as isotactic or syndiotactic structure.In above-mentioned metallocene compound, suitable use is disclosed the bridging property metallocene compound of (WO01/27124) by international application by the application's applicant.
Figure A200780029515D00181
In above-mentioned general formula [I], R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14Be selected from hydrogen, alkyl, contain silica-basedly, can be the same or different respectively.As such alkyl, can enumerate straight chain shape alkyl such as methyl, ethyl, n-propyl, allyl group, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl; Sec.-propyl, the tertiary butyl, amyl group, 3-methyl amyl, 1,1-diethyl propyl group, 1,1-dimethylbutyl, 1-methyl isophthalic acid-propyl group butyl, 1,1-propyl group butyl, 1, a chain alkyl such as 1-dimethyl-2-methyl-propyl, 1-methyl isophthalic acid-sec.-propyl-2-methyl-propyl; Cyclic saturated hydrocarbon bases such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norcamphyl, adamantyl; Ring-type unsaturated alkyls such as phenyl, tolyl, naphthyl, xenyl, phenanthryl, anthryl; Benzyl, cumyl, 1, the saturated hydrocarbyl that ring-type unsaturated alkyls such as 1-diphenyl-ethyl, trityl group replace; Methoxyl group, oxyethyl group, phenoxy group, furyl, N-methylamino-, N, N-dimethylamino, N-phenyl amino, pyrryl, thienyl etc. contain heteroatomic alkyl etc.Silica-based as containing, can enumerate trimethyl silyl, triethylsilyl, 3,5-dimethylphenyl silyl, diphenyl methyl silyl, triphenyl silyl etc.And, R 5～R 12The substituting group of adjacency can mutually combine and form ring.As such replacement fluorenyl, can enumerate benzo fluorenyl, dibenzo fluorenyl, octahydro dibenzo fluorenyl, prestox octahydro dibenzo fluorenyl, prestox tetrahydrochysene two cyclopentyl fluorenyls etc.
In above-mentioned general formula [I], the R that on cyclopentadienyl rings, replaces 1, R 2, R 3, R 4Be preferably the alkyl of hydrogen or carbonatoms 1～20.As the alkyl of carbonatoms 1～20, can the above-mentioned alkyl of illustration.More preferably R 3Alkyl for carbonatoms 1～20.
In above-mentioned general formula [I], at the nuclear substituted R of fluorenes 5～R 12Be preferably the alkyl of carbonatoms 1～20.As the alkyl of carbonatoms 1～20, can the above-mentioned alkyl of illustration.R 5～R 12The substituting group of adjacency can mutually combine and form ring.
In above-mentioned general formula [I], make the crosslinked Y of cyclopentadienyl rings and fluorenes ring be preferably IVA family element, more preferably carbon, silicon, germanium, more preferably carbon atom.The R that on this Y, replaces 13, R 14Be preferably the alkyl of carbonatoms 1～20.These can be the same or different mutually, can also mutually combine to form ring.As the alkyl of carbonatoms 1～20, can the above-mentioned alkyl of illustration.More preferably R 14Aryl (aryl) for carbonatoms 6～20.As aryl, can enumerate saturated hydrocarbyl that above-mentioned ring-type unsaturated alkyl, ring-type unsaturated alkyl replace, contain heteroatomic ring-type unsaturated alkyl.And, R 13, R 14Can be the same or different respectively, can also mutually combine forms ring.As such substituting group, preferred fluorenylidene, 10-hydrogen anthrylene (10-hydro anthracenylidene), the inferior cycloheptadiene base of dibenzo (dibenzocycloheptadienylidene) etc.
In above-mentioned general formula [I], M is preferably the IVB group 4 transition metal, more preferably enumerates Ti, Zr, Hf etc.In addition, Q is selected from halogen, alkyl, anion ligand or can be with the identical or different combination in the lone-pair electron coordinate neutral ligand.J is 1～4 integer, and when j is 2 when above, Q can be the same or different mutually.As the object lesson of halogen, be fluorine, chlorine, bromine, iodine.As the object lesson of alkyl, can enumerate alkyl same as described above etc.As the object lesson of anion ligand, can enumerate alkoxyl groups such as methoxyl group, tert.-butoxy, phenoxy group, carboxylic acid ester groups such as acetate groups, phenylformic acid ester group, sulfonate groups such as methylsulfonic acid ester group, toluenesulphonic acids ester group etc.As can be with the object lesson of lone-pair electron coordinate neutral ligand, can enumerate organo phosphorous compoundss such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine, tetrahydrofuran (THF), diethyl ether, diox, 1, ethers such as 2-glycol dimethyl ether etc.Preferably at least one is halogen or alkyl to Q.
As so crosslinked metallocene compound, preferred isopropylidene (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride that uses, isopropylidene (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride.
In addition, also can compatibly use the metallocene compound shown in the following general formula [II].
Figure A200780029515D00201
In general formula [II], R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16Be selected from hydrogen atom, the former subbase of hydrocarbon, contain silica-basedly, can be the same or different respectively.R 1～R 16The substituting group of adjacency can mutually combine and form ring.But R 2It or not aryl.Wherein, so-called here aryl refers to conjugation sp in aromatic hydrocarbyl 2Have free valent substituting group on the carbon, for example phenyl, tolyl, naphthyl etc. do not comprise benzyl and styroyl, phenyl dimetylsilyl etc.As alkyl, can enumerate straight chain shape alkyl such as methyl, ethyl, n-propyl, allyl group, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl; Sec.-propyl, the tertiary butyl, amyl group, 3-methyl amyl, 1,1-diethyl propyl group, 1,1-dimethylbutyl, 1-methyl isophthalic acid-propyl group butyl, 1,1-propyl group butyl, 1, a chain alkyl such as 1-dimethyl-2-methyl-propyl, 1-methyl isophthalic acid-sec.-propyl-2-methyl-propyl; Cyclic saturated hydrocarbon bases such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norcamphyl, adamantyl, methylcyclohexyl, methyl adamantane base; Ring-type unsaturated alkyls such as phenyl, tolyl, naphthyl, xenyl, phenanthryl, anthryl; Benzyl, cumyl, 1, the saturated hydrocarbyl that ring-type unsaturated alkyls such as 1-diphenyl-ethyl, trityl group replace; Methoxyl group, oxyethyl group, phenoxy group, furyl, N-methylamino-, N, N-dimethylamino, N-phenyl amino, pyrryl, thienyl etc. contain heteroatomic alkyl etc.Silica-based as containing, can enumerate trimethyl silyl, triethylsilyl, 3,5-dimethylphenyl silyl, diphenyl methyl silyl, triphenyl silyl etc.And, the R of fluorenes ring 9～R 16The substituting group of adjacency can mutually combine and form ring.As such replacement fluorenyl, can enumerate benzo fluorenyl, dibenzo fluorenyl, octahydro dibenzo fluorenyl, prestox octahydro dibenzo fluorenyl, prestox tetrahydrochysene two cyclopentyl fluorenyls etc.
In above-mentioned general formula [II], R 1And R 3Be preferably hydrogen atom.Also be preferably selected from R 6And R 7In at least one be hydrogen atom, more preferably R 6And R 7It all is hydrogen atom.
In above-mentioned general formula [II], the R that on cyclopentadienyl rings, replaces 2Not aryl, be preferably the alkyl of hydrogen atom or carbonatoms 1～20.As the alkyl of carbonatoms 1～20, can the above-mentioned alkyl of illustration.As R 2, be preferably alkyl, be preferably methyl, ethyl, sec.-propyl, the tertiary butyl, be preferably the tertiary butyl especially.
R 4And R 5Be selected from the alkyl and the aryl of hydrogen atom, carbonatoms 1～20, be preferably the alkyl of carbonatoms 1～20.More preferably R 4And R 5Be selected from methyl and phenyl, preferred especially R4 and R 5Identical.
In above-mentioned general formula [II], the R on the preferred fluorenes ring 9, R 12, R 13And R 16Be hydrogen atom.
In above-mentioned general formula [II], M is the IVB group 4 transition metal, specifically can enumerate Ti, Zr, Hf etc.In addition, the Q cohort that is selected from halogen atom, the former subbase of hydrocarbon, anion ligand or can constitutes with lone-pair electron coordinate neutral ligand.J is 1～4 integer, and when j is 2 when above, Q can be the same or different mutually.As the object lesson of halogen atom, be fluorine, chlorine, bromine, iodine.As the object lesson of alkyl, can enumerate alkyl same as described above.Object lesson as anion ligand, can enumerate alkoxyl groups such as methoxyl group, tert.-butoxy, phenoxy group, carboxylic acid ester groups such as acetate groups, phenylformic acid ester group, amide group such as sulfonate groups such as methylsulfonic acid ester group, toluenesulphonic acids ester group, dimethylformamide, diisopropylamide, methyl anilide, phenylbenzene acid amides etc.As can be with the object lesson of lone-pair electron coordinate neutral ligand, can enumerate organo phosphorous compoundss such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine, tetrahydrofuran (THF), diethyl ether, diox, 1, ethers such as 2-glycol dimethyl ether etc.Preferably at least one is halogen atom or alkyl to Q.
As the metallocene compound shown in the above-mentioned general formula of the present invention [II], can illustration [3-(fluorenyl) (1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1,1,3,5-tetramethyl--1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1,3,5-tetramethyl--1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1,3,5-tetramethyl--1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1,3,5-tetramethyl--1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(fluorenyl) (1, the 1-dimethyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1, the 1-dimethyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1-dimethyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1-dimethyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1,1,3-triethyl-2-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1,3-triethyl-2-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1,3-triethyl-2-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1,3-triethyl-2-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1, the 3-dimethyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,3-dimethyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1, the 3-dimethyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1, the 3-dimethyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(fluorenyl) (1,1,3-trimethylammonium-5-ethyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1,3-trimethylammonium-5-ethyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1,3-trimethylammonium-5-ethyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1,3-trimethylammonium-5-ethyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1,1,3-trimethylammonium-5-trimethyl silyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1,3-trimethylammonium-5-trimethyl silyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1,3-trimethylammonium-5-trimethyl silyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1,3-trimethylammonium-5-trimethyl silyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(the fluorenyl) (3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (3-methyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (3-methyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride,
[3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (3-methyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1-phenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1-phenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1-phenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1-phenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1-p-methylphenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1-p-methylphenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1-p-methylphenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1-p-methylphenyl-3-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(fluorenyl) (1, the 3-phenylbenzene-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,3-phenylbenzene-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1, the 3-phenylbenzene-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1, the 3-phenylbenzene-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride,
[3-(fluorenyl) (1,3-phenylbenzene-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,3-phenylbenzene-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,3-phenylbenzene-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride,
[3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,3-phenylbenzene-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1,3-two (p-methylphenyl)-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,3-two (p-methylphenyl)-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,3-two (p-methylphenyl)-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,3-two (p-methylphenyl)-1-methyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(the fluorenyl) (3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (3-phenyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (3-phenyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (3-phenyl-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1-methyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1-methyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1-methyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1-methyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1,1-dimethyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1-dimethyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride;
[3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1-dimethyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4,7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1-dimethyl-3-phenyl-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] hafnium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] hafnium dichloride;
[3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] hafnium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1,3-trimethylammonium-5-the tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] hafnium dichloride, [3-(fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] titanium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] titanium dichloride;
[3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] titanium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] titanium dichloride
As particularly preferred compound, can illustration [3-(fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(3 ', 6 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride, [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride.
But metallocene compound of the present invention [m] is not limited to above-mentioned illustrative compound fully, comprises the whole compounds that satisfy the important document that defines in the application's claim.Wherein, with [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride and [3-(2 ', 7 '-the di-t-butyl fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride is an example, respectively at following formula [II '] with [be illustrated in the position number that uses in the name of above-claimed cpd among the II "].
Figure A200780029515D00251
Figure A200780029515D00252
In addition, in metallocene catalyst of the present invention, for with the IVB group transition metal compound shown in above-mentioned general formula [I], [II] use simultaneously be selected from organometallic compound, Organoaluminoxy compound and can with at least a kind of compound in the right compound of transistion metal compound reacting forming ion, and the granular carrier that uses as required, can unrestrictedly use disclosed compound in above-mentioned communique (WO01/27124) or 11-No. 315109 communiques of Japanese patent laid-open by the applicant.
(7) sheet material or film
Sheet material of the present invention or film are sheet material or the films that is obtained by above-mentioned propylene resin composition for packaging material of the present invention.
This sheet material or film can use propylene resin composition for packaging material, with various known forming methods, for example use the film shaper manufacturing that has T mould or a circular mode at the forcing machine front end to form.
The thickness of sheet material of the present invention or film can be done various decisions according to purposes, but usually in the scope of 10 μ m～2mm, preferably in the scope of 10～200 μ m.Even the film that film of the present invention is thin as a comparison, the shock-resistance during low temperature are also excellent.
Sheet material of the present invention or film can be unstretching film, also can be stretched film, but preferred stretchable film not.
Sheet material of the present invention or film, even individual layer also can use with wrapping material such as films as boiling, but by with stretch or laminations such as stretched polyamide film, single shaft or biaxially oriented polyester film, aluminium foil or paper not, can use with film as the multiwalled boiling.In addition, by making individual layer and multiwalled protective membrane, can use as optical sheet or metallic surface protecting materials.And, also can use with material as medical wrapping material or Freshkeeping Packaging.Particularly as the Freshkeeping Packaging material, the propylene resin composition for packaging material of second form is fit to.
Embodiment
Below, explain the present invention based on embodiment, but the present invention is not limited to these embodiment.The analytical procedure that adopts among the present invention is as follows.
[m1] MFR (melt flow rate (MFR))
MFR measures according to ASTM D1238 (230 ℃, load 2.16kg).
[m2] Fusing point (Tm)
Use differential scanning calorimeter (DSC, PerkinElmer company produce) to measure.Here, the endotherm(ic)peak with the 3rd stage is defined as fusing point (Tm).
(condition determination)
The 1st stage: be warmed up to 240 ℃ with 10 ℃/min, keep 10min.
The 2nd stage: cool to 60 ℃ with 10 ℃/min.
The 3rd stage: be warmed up to 240 ℃ with 10 ℃/min.
[m3] Limiting viscosity [η]
Use the naphthane solvent, measure at 135 ℃.The about 20mg sample of dissolving in the 15ml naphthane is measured specific viscosity η sp in 135 ℃ oil bath.In this naphthane solution, append 5ml naphthane solvent cut, same then time-and-motion study specific viscosity η sp.Should dilution operate for 2 times repeatedly, the value that concentration (C) is extrapolated to 0 o'clock η sp/C is obtained as limiting viscosity again.
[η]＝lim(ηsp/C) (C→0)
[m4] Mw/Mn measures [weight-average molecular weight (Mw), number-average molecular weight (Mn)]
The following operation of GPC-150C Plus of using Waters company to produce is measured.Separator column is TSKgel GMH6-HT and TSKgel GMH6-HTL, column dimension is respectively internal diameter 7.5mm, length 600mm, column temperature is 140 ℃, moving phase is used orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.) and as BHT (Wako Pure Chemical Industries, Ltd.) the 0.025 weight % of antioxidant, moved with 1.0ml/ minute, sample solution concentration is 0.1 weight %, and the sample injection rate is 500 microlitres, uses differential refractometer as detector.Polystyrene standard is Mw＜1000 and Mw for molecular weight〉4 * 10 6Use the goods of TOSOH company, for 1000≤Mw≤4 * 10 6Use the goods of Pressure Chemical company, adopt universal calibration method to be scaled PP.Wherein, the Mark-Houwink coefficient of PS, PP uses the value of record in the document (J.Polym.Sci., Part A-2,8,1803 (1970), Makromol.Chem., 177,213 (1976)) respectively.
[m5] is at 23 ℃ of amount (D that dissolve in the part of n-decane Sol )
In 5g end product (being the Propenes resin composition that uses among the present invention) sample, add the 200ml n-decane, 145 ℃ of heating for dissolving 30 minutes.Be cooled to 23 ℃ with about 3 hours, placed 30 minutes.Then, (following be at the 23 ℃ of part that is insoluble to n-decane: D to the filtering separation precipitate Insol).Filtrate is added in the acetone of about 3 times of amounts, the one-tenth that is dissolved in the n-decane is analyzed.Filtering separation precipitate (A) and acetone, dry precipitate.In addition, even, can not confirm to have residue with filtrate side concentrate drying.Obtain by following formula 23 ℃ of amounts that dissolve in the part of n-decane.
23 ℃ of amount (weight %)=[precipitate (A) weight/example weight] * 100 that dissolve in the part of n-decane
[m6] Content from the structural unit of ethene
In order to measure propylene-ethylene copolymer (B) and D Insol, D SolIn the concentration from the structural unit of ethene, with 20～30mg sample dissolution at 1,2 of 0.6ml, in 4-trichlorobenzene/heavy benzol (2: 1) solution, carry out then the nuclear magnetic resonance of carbon analysis ( 13C-NMR).Propylene, ethene, quantitatively being distributed by the binary chain of alpha-olefin are obtained.For example, under the situation of propylene-ethylene copolymer, use PP=S α α, EP=S α γ+S α β, EE=1/2 (S β δ+S δ δ)+1/4S γ δ, obtain by following calculating formula (Eq-1) and (Eq-2).
Propylene (mol%)=(PP+1/2EP) * 100/[(PP+1/2EP)+(1/2EP+EE) ... (Eq-1)
Ethene (mol%)=(1/2EP+EE) * 100/[(PP+1/2EP)+(1/2EP+EE) ... (Eq-2)
Wherein, the D in the present embodiment InsolThe ethene amount and the unit conversion of alpha-olefin amount be weight % record.
[m7] 2,1-inserts binding capacity, 1, and 3-inserts binding capacity
At 1,2 of 0.6ml, dissolve 20～30mg sample in 4-trichlorobenzene/heavy benzol (2: 1) solution, carry out then the nuclear magnetic resonance of carbon analysis ( 13C-NMR).With 2,1-inserts the monomer that forms and form the position irregular unit shown in the above-mentioned part-structure (i) in polymer chain.With respect to 2 of whole propylene insertions, 1-propylene monomer insertion amount is calculated by following formula.
Based on 2, the ratio of the position irregular unit that 1-inserts
Figure A200780029515D00281
In the formula, ∑ ICH 3The area of representing whole methyl.In addition, I α δ and I β γ represent near α β peak ('s resonating the 37.1ppm) area, the area at β γ peak (resonating) respectively near 27.3ppm.Wherein, the name of these methylene peak according to the method for Carman etc. (RubberChem.Technol., 44(1971), 781) carry out.
Equally, the above-mentioned part-structure that inserts with respect to whole propylene 1 shown in (ii), 3-propylene monomer insertion amount is calculated by following formula.
Based on 1, the ratio (%) of the position irregular unit that 3-inserts
Figure A200780029515D00282
[m8] density
The density measurement of ethene-alpha-olefin copolymer 120 ℃ of thermal treatments 1 hour, with 1 hour straight line cool to room temperature slowly, is measured working sample then with density gradient tube.
[m9] The rigidity of film
According to JIS K 6781, measure the modulus in tension of film, estimate rigidity.
＜test conditions 〉
Temperature: 23 ℃
Draw rate: 200mm/min
Distance between chuck: 80mm
[m10] The shock-resistance of film
Film is sampled as 5cm * 5cm, under specified temperature, measures the face shock strength, estimate shock-resistance with shock test (mode that hammer is collided from bottom to top).
＜test conditions 〉
Temperature :-10 ℃
Hammer: 1 inch of front end, load 3.0J
[m11] The mist degree of film (HAZE)
Measure according to ASTM D-1003.
[m12] The resistance to blocking of film
The cooling roll surface of the film of MD direction 10cm * TD direction 10cm is overlapped each other, in 50 ℃ thermostatic bath with 200g/cm 2Load kept 3.Then, 23 ℃, the indoor status adjustment of carrying out more than 24 hours of humidity 50%, measure the stripping strength when making it to peel off with draw rate 200mm/min then, the value that will obtain divided by the test film width with stripping strength is estimated resistance to blocking as the adhesion coefficient.Wherein, the adhesion coefficient is more little, and resistance to blocking is excellent more.
[m13] The heat seal strength of film
Film is sampled as the 5mm width, seals with 1 second heat-sealing time, heat-sealing pressure 0.2MPa.With the two ends of the film of 300mm/min tractive sealing, measure the maximum strength of peeling off.Wherein, seal bar top is set at 200 ℃ assigned temperature, temperature of lower is set at 70 ℃.
[m14] The gas-premeable of film
Use the smart mechanism of Toyo Co., Ltd. to make gas permeation rate determinator MT-C3 type of being produced,, measure with 23 ℃, the condition of 0%RH according to the A method of JIS K7126.
[m15] The temperature dependency of Young's modulus
As stable on heating index, measure the temperature dependency of Young's modulus according to following condition.Particularly, pellet is made the moulding product, carry out temperature dispersion with solid determination of viscoelasticity device and measure with compression moulding.
Determinator: RSA-II (TA production)
Mode determination: tractive pattern (Autotension, Autostrain control)
Measure temperature :-80～150 ℃ (to the temperature that can measure)
Heat-up rate: 3 ℃/min
Specimen size: wide 5mm * thick 0.4mm
Initial stage Gap (L 0): 21.5mm
Atmosphere gas: N 2
(the manufacturing of C2-1a) of [Production Example 1a] propylene-based block copolymer
(1) manufacturing of solid catalyst carrier
The SiO of sampling 300g in the distilling flask of 1L 2, add 800mL toluene, carry out slurryization, move the 4 mouthful flasks of liquid then to 5L, add 260mL toluene.Add the toluene solution (10 weight % solution) of 2830mL methylaluminoxane (following is MAO), at room temperature stirred 30 minutes.Be warmed up to 110 ℃ with 1 hour, reacted 4 hours.Reaction cools to room temperature after finishing.After the cooling, removing supernatant toluene liquid, add toluene again and replace, is 95% until rate of displacement.
(2) manufacturing of solid catalyst (the metal catalyst composition is held to carrying of carrier)
In glove box, in 4 mouthfuls of flasks of 5L, take by weighing 2.0g [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride.Flask is moved to the outside, under nitrogen, add 0.46 liter of toluene and 1.4 liters of modulated M AO/SiO in (1) 2/ toluene slurry stirs to carry in 30 minutes and holds.Obtain [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride/MAO/SiO 2/ toluene slurry carries out 99% displacement with normal heptane, and making final amount of slurry is 4.5 liters.This operates in room temperature and carries out.
(3) manufacturing of prepolymerization catalyst
In the autoclave of the band stirrer of internal volume 200L, import 404g synthetic solid catalyst component, 218mL triethyl aluminum, 100L heptane in above-mentioned (2), temperature is at 15～20 ℃ in keeping, import 1212g ethene, made it reaction in 180 minutes while stir.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 4g/L with solid catalyst component concentration.This prepolymerization catalyst, every 1g solid catalyst component contains the 3g polyethylene.
(4) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 3.5g/ and hour supply with the catalyst pulp of in above-mentioned (3), making, 2.3ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.2mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the tubular stinger of internal volume 2.4L, makes it gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.52 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.1MPa/G.
With the propylene-based block copolymer that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of C2-2a) of [Production Example 2a] propylene-based block copolymer
Except with the following variation of polymerization process, use the method manufacturing propylene resin composition for packaging material same with Production Example 1a.
(1) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 6.2g/ and hour supply with the catalyst pulp of among Production Example 1a (3), making, 2.3ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 1NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is transferred to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.09mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is sent to the tubular stinger of internal volume 2.4L, makes it gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.10 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.1MPa/G.
With the propylene-based block copolymer that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of C2-3a) of [Production Example 3a] propylene-based block copolymer
Except with the following variation of polymerization process, use the method manufacturing propylene-based block copolymer same with Production Example 1a.
(1) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 6.2g/ and hour supply with the catalyst pulp of among Production Example 1a (3), making, 2.3ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 1NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.09mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the tubular stinger of internal volume 2.4L, makes it gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.10 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.9MPa/G.
With the propylene-based block copolymer that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of C2-4a) of [Production Example 4a] propylene-based block copolymer
Except with the following variation of polymerization process, use the method manufacturing propylene-based block copolymer same with Production Example 1a.
(1) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 6.2g/ and hour supply with the catalyst pulp of among Production Example 1a (3), making, 2.3ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 1NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.09mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the tubular stinger of internal volume 2.4L, makes it gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.20 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.0MPa/G.
With the propylene-based block copolymer that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of C2-5a) of [Production Example 5a] propylene-based block copolymer
The solid catalyst carrier that use is made in Production Example 1a (1) is made propylene-based block copolymer with following method.
(1) manufacturing of solid catalyst (the metal catalyst composition is held to carrying of carrier)
In glove box, in 4 mouthfuls of flasks of 5L, take by weighing phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2, the 7-tertiary butyl fluorenyl) zirconium dichloride of 2.0g.Flask is moved to the outside, under nitrogen, add 0.46 liter of toluene and 1.4 liters of modulated M AO/SiO in (1) 2/ toluene slurry stirs to carry in 30 minutes and holds.The phenylbenzene methylene radical that obtains (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-tertiary butyl fluorenyl) zirconium dichloride/MAO/SiO 2/ toluene slurry carries out 99% displacement with normal heptane, and making final amount of slurry is 4.5 liters.This operates in room temperature and carries out.
(2) manufacturing of prepolymerization catalyst
Import 404g synthetic solid catalyst component, 218mL triethyl aluminum, 100L heptane in above-mentioned (1) in the autoclave of the band stirrer of internal volume 200L, temperature imports 606g ethene at 15～20 ℃ in keeping, and stirs on one side to make it in 180 minutes to react.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 4g/L with solid catalyst component concentration.This prepolymerization catalyst, every 1g solid catalyst component contains the 3g polyethylene.
(3) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 10.0g/ and hour supply with the catalyst pulp of in above-mentioned (2), making, 2.3ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 1NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.05mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the tubular stinger of internal volume 2.4L, makes it gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.10 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.1MPa/G.
With the propylene-based block copolymer that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of C2-6a) of [Production Example 6a] propylene-based block copolymer
The solid catalyst carrier that use is made in Production Example 1a (1) is made propylene-based block copolymer with following method.
(1) manufacturing of solid catalyst (the metal catalyst composition is held to carrying of carrier)
In glove box, in 4 mouthfuls of flasks of 5L, take by weighing silica-based pair-(2-methyl-4-phenyl indenyl) zirconium dichloride of dimethylated methylene of 2.0g.Flask is moved to the outside, under nitrogen, add 0.46 liter of toluene and 1.4 liters of modulated M AO/SiO in (1) 2/ toluene slurry stirs to carry in 30 minutes and holds.Silica-based couple-(2-methyl-4-phenyl indenyl) zirconium dichloride/MAO/SiO of the dimethylated methylene that obtains 2/ toluene slurry carries out 99% displacement with normal heptane, and making final amount of slurry is 4.5 liters.This operates in room temperature and carries out.
(2) manufacturing of prepolymerization catalyst
Import 202g synthetic solid catalyst component, 109mL triethyl aluminum, 100L heptane in above-mentioned (1) in the autoclave of the band stirrer of internal volume 200L, temperature imports 606g ethene at 15～20 ℃ in keeping, and stirs on one side to make it in 180 minutes to react.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 2g/L with solid catalyst component concentration.This prepolymerization catalyst, every 1g solid catalyst component contains the 3g polyethylene.
(3) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 1.2g/ and hour supply with the catalyst pulp of in above-mentioned (2), making, 2.3ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.14mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the tubular stinger of internal volume 2.4L, makes it gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.45 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.7MPa/G.
With the propylene-based block copolymer that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of A-1a) of [Production Example 7a] acronal
The solid catalyst carrier that use is made in Production Example 1a (1) is made acronal with following method.
(1) manufacturing of solid catalyst (the metal catalyst composition is held to carrying of carrier)
In glove box, in 4 mouthfuls of flasks of 5L, take by weighing dimethylated methylene base (the 3-tertiary butyl-5-methyl cyclopentadienyl) (3, the 6-di-t-butyl fluorenyl) zirconium dichloride of 2.0g.Flask is moved to the outside, under nitrogen, add 0.46 liter of toluene and 1.4 liters of modulated M AO/SiO in (1) 2/ toluene slurry stirs to carry in 30 minutes and holds.The dimethylated methylene base that obtains (the 3-tertiary butyl-5-methyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride/MAO/SiO 2/ toluene slurry carries out 99% displacement with normal heptane, and making final amount of slurry is 4.5 liters.This operates in room temperature and carries out.
(2) manufacturing of prepolymerization catalyst
Import 202g synthetic solid catalyst component, 109mL triethyl aluminum, 100L heptane in above-mentioned (1) in the autoclave of the band stirrer of internal volume 200L, temperature imports 606g ethene at 15～20 ℃ in keeping, and stirs on one side to make it in 180 minutes to react.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 2g/L with solid catalyst component concentration.This prepolymerization catalyst, every 1g solid catalyst component contains the 3g polyethylene.
(3) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 8.0g/ and hour supply with the catalyst pulp of in above-mentioned (2), making, 5.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 3NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 1000L, carries out polymerization again.Supplied with propylene to polymerizer with 160kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.07mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 500L, carries out polymerization again.Supplied with propylene to polymerizer with 16kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.07mol%.Carry out polymerization with 69 ℃ of polymerization temperatures, pressure 2.9MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 500L, carries out polymerization again.Supplied with propylene to polymerizer with 12kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.07mol%.Carry out polymerization with 68 ℃ of polymerization temperatures, pressure 2.9MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 500L, carries out polymerization.Supplied with propylene to polymerizer with 17kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.07mol%.Carry out polymerization with 67 ℃ of polymerization temperatures, pressure 2.8MPa/G.
After the slurry gasification that obtains, carry out gas solid separation, obtain acronal.With the acronal that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of A-2a) of [Production Example 8a] acronal
Except with the following variation of polymerization process, use the method manufacturing acronal same with Production Example 5a.
(1) main polymerization
Continuously in the tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 7.1g/ and hour supply with the catalyst pulp of in pre-polymerization, making as solid catalyst component, 4.0mL/ and hour supply with triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase to supply with propylene, 4NL/ in 57kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 2.6MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 1000L, carries out polymerization again.Supplied with propylene, 1.7kg/ hour supply ethene to polymerizer with 50kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.16mol%.Carry out polymerization with 60 ℃ of polymerization temperatures, pressure 2.5MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 500L, carries out polymerization again.Supplied with propylene, 1.2kg/ hour supply ethene to polymerizer with 11kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.16mol%.Carry out polymerization with 59 ℃ of polymerization temperatures, pressure 2.4MPa/G.
After the slurry gasification that obtains, carry out gas solid separation, obtain acronal.With the acronal that obtains 80 ℃ of vacuum-dryings.
(the manufacturing of B-1a) of [Production Example 9a] propylene-ethylene copolymer
Except with the following variation of polymerization process, use the method manufacturing propylene-ethylene copolymer same with Production Example 5a.
(1) main polymerization
Fully replace and be to add the 9kg liquid propene in 10 ℃ the SUS system autoclave of internal volume 30L at nitrogen, add the ethene of 0.5MPa as dividing potential drop.Fully stir on one side on one side and be warmed up to 45 ℃, import with tube from catalyzer, pressurizeing in autoclave with nitrogen imports the mixing solutions of 0.6g solid catalyst component/300ml heptane and 0.5ml triethyl aluminum.Carry out polymerization in 20 minutes at 60 ℃, add methyl alcohol then, stop polymerization.After polymerization finishes, remove propylene, fully carry out nitrogen replacement, isolating polymer.With propylene-ethylene copolymer of obtaining 80 ℃ of vacuum-dryings.
(the manufacturing of B-2a) of [Production Example 10a] propylene-ethylene copolymer
(1) modulation of solid titanium catalyst component
952g Magnesium Chloride Anhydrous, 4420ml decane and 3906g 2-Ethylhexyl Alcohol 130 ℃ of heating 2 hours, are obtained homogeneous solution.In this solution, add the 213g Tetra hydro Phthalic anhydride, mixed 1 hour at 130 ℃ again, make the Tetra hydro Phthalic anhydride dissolving.
The homogeneous solution that obtains of operation like this is cooled to 23 ℃, remained on this solution of dropping 750ml in-20 ℃ the titanium tetrachloride then with 1 hour at 2000ml.After the dropping, be warmed up to 110 ℃, when arriving 110 ℃, add 52.2g diisobutyl phthalate (DIBP), while and stir and kept this temperature in 2 hours with 4 hours temperature with the mixed solution that obtains.Then, filter when hot and gather solid part, make this solid part outstanding more turbid in the 2750ml titanium tetrachloride, and then 110 ℃ of heating 2 hours.
Heating is gathered solid part with heat filtering after finishing once more, uses 110 ℃ decane and hexane to clean, and can't detect titanium compound in scavenging solution.
Above-mentioned synthetic solid titanium catalyst component is preserved with the hexane slurry, dry its part, and the research catalyzer is formed.Solid titanium catalyst component contains the titanium of 2 weight %, the chlorine of 57 weight %, the magnesium of 21 weight % and the DIBP of 20 weight %.
(2) manufacturing of prepolymerization catalyst
Import 56g transition metal catalyst component, 9.8mL triethyl aluminum, 80L heptane in the autoclave of the band stirrer of internal volume 200L, temperature imports the 560g propylene at 5 ℃ in keeping, and stirs on one side to make it in 60 minutes to react.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 1.0g/L with transition metal catalyst component concentration.This prepolymerization catalyst, every 1g transition metal catalyst component contains the 10g polypropylene.
(3) main polymerization
In the SUS of the abundant metathetical internal volume of nitrogen 30L system autoclave, add the 9kg liquid propene, fully stir on one side and be warmed up to 45 ℃ on one side.Add the ethene of 0.15MPa, the hydrogen of 20NL as dividing potential drop.Import with tube from catalyzer, pressurizeing in autoclave with nitrogen imports the mixing solutions of 0.2g solid catalyst component/200ml heptane and 2.0ml triethyl aluminum and 0.4ml dicyclopentyl dimethoxyl silane.Carry out polymerization in 15 minutes at 50 ℃, add methyl alcohol then, stop polymerization.After polymerization finishes, remove propylene, fully carry out nitrogen replacement, isolating polymer.Carry out vacuum-drying at 80 ℃.(the ethene amount of B-2a) is that 20mol%, limiting viscosity [η] are 2.1dl/g to the propylene-ethylene copolymer that obtains.
[embodiment 1a]
With respect to the propylene-based block copolymer of in Production Example 1a, making of 100 weight parts (C2-1a), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (production of Cibaspecialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (production of Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (production of silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the propylene resin composition for packaging material of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 2.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[embodiment 2a]
(C2-1a) replaces with the propylene-based block copolymer of making of 100 weight parts in Production Example 2a (C2-2a), in addition, casting films is made in same operation with the propylene-based block copolymer of 100 weight parts among the embodiment 1a.The rerum natura of the film that expression obtains in table 2.
[embodiment 3a]
((D-1a) (Engage 8003 (registered trademark): dupon dow elastomer Co., Ltd. produces the ethene-octene copolymer of C2-3a) and 5 weight parts, density=0.885 (g/cm with respect to the propylene-based block copolymer of making in Production Example 3a of combination 95 weight parts 3)) 100 weight parts, utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (production of Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (production of Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (production of silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the Propenes resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 2.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[embodiment 4a]
(D-1a) (Engage8003 (registered trademark): dupon dow elastomer Co., Ltd. produces, density=0.885 (g/cm with the ethene-octene copolymer of 5 weight parts among the embodiment 3a 3)) ((Engage 8480 (registered trademark): dupon dow elastomer Co., Ltd. produces, density=0.902 (g/cm for D-2a) to replace with the ethene-octene copolymer of 5 weight parts 3)), in addition, casting films is made in same operation.The rerum natura of the film that expression obtains in table 2.
[embodiment 5a]
(D-1a) (Engage 8003 (registered trademark): dupon dow elastomer Co., Ltd. produces, density=0.885 (g/cm with the ethene-octene copolymer of 5 weight parts among the embodiment 3a 3)) ((Engage 8100 (registered trademark): dupon dow elastomer Co., Ltd. produces, density=0.870 (g/cm for D-3a) to replace with the ethene-octene copolymer of 5 weight parts 3)), in addition, casting films is made in same operation.The rerum natura of the film that expression obtains in table 2.
[embodiment 6a]
(C2-1a) replaces with the propylene-based block copolymer of making of 100 weight parts in Production Example 5a (C2-5a), in addition, casting films is made in same operation with the propylene-based block copolymer of 100 weight parts among the embodiment 1a.The rerum natura of the film that expression obtains in table 2.
[embodiment 7a]
With respect to the acronal of in Production Example 7a, making of the combination 80 weight parts (propylene-ethylene copolymer of in Production Example 9a, making of A-1a) and 20 weight parts (100 weight parts of B-1a), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (production of Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (production of Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (production of silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the Propenes resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 2.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[embodiment 8a]
(A-1a) replaces with alfon (A-3a) (production of F102W:prime polymer Co., Ltd.) made from ziegler-natta catalyzer class of 80 weight parts with the acronal of 80 weight parts among the embodiment 7a, in addition, casting films is made in same operation.The rerum natura of the film that expression obtains in table 2.
[comparative example 1a]
(B-1a) replaces with the acronal of making of 20 weight parts in Production Example 8a (A-2a), in addition, casting films is made in same operation with the propylene-ethylene copolymer of 20 weight parts among the embodiment 7a.The rerum natura of the film that expression obtains in table 2.
[comparative example 2a]
(C2-1a) replaces with the propylene-based block copolymer of making of 100 weight parts in Production Example 4a (C2-4a), in addition, casting films is made in same operation with the propylene-based block copolymer of 100 weight parts among the embodiment 1a.The rerum natura of the film that expression obtains in table 2.
[comparative example 3a]
(C2-1a) replaces with the propylene-based block copolymer of making of 100 weight parts in Production Example 6a (C2-6a), in addition, casting films is made in same operation with the propylene-based block copolymer of 100 weight parts among the embodiment 1a.The rerum natura of the film that expression obtains in table 2.
[comparative example 4a]
With respect to the acronal of the combination 80 weight parts (propylene-ethylene copolymer of in Production Example 10a, making of A-3a) (production of F102W:primepolymer Co., Ltd.) and 20 weight parts (100 weight parts of B-2a), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (production of Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (production of Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (production of silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the Propenes resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 2.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
Figure A200780029515D00431
Figure A200780029515D00441
By embodiment 1a, embodiment 2a and comparative example 2a, at following expression D SolIn C2 amount influence the effect of film rerum natura.Embodiment 1a and embodiment 2a comprise D SolC2 amount be the propylene resin composition for packaging material of the propylene-based block copolymer of 20mol%.If with comprise D SolC2 amount compare for the comparative example 2a of the propylene resin composition for packaging material of the propylene-based block copolymer of 30mol%, the resistance to blocking of embodiment 1a and embodiment 2a and the transparency are excellent as can be known.
By embodiment 6a and comparative example 3a, at following expression D SolIn [η] influence the effect of film rerum natura.Embodiment 6a comprises D Sol[η] be the propylene resin composition for packaging material of the propylene-based block copolymer of 2.1dl/g.If with comprise D Sol[η] compare the D of embodiment 6a as can be known for the comparative example 3a of the propylene resin composition for packaging material of the propylene-based block copolymer of 1.0dl/g Sol[η] high, impact strength is excellent.
Embodiment 7a is the propylene resin composition for packaging material that comprises acronal A1-a and propylene-ethylene copolymer B1-a, be with embodiment 2a in the proximate resin combination of propylene-based block copolymer C2-2a put down in writing.Here, embodiment 7a and embodiment 2a have almost equal good film rerum natura.Therefore, by propylene resin composition for packaging material of the present invention,, just can not access the transparency, impact strength, the film of resistance to blocking excellence, sheet material by the melting mixing method of propene polymer and propylene-ethylene copolymer, the polymerization manufacturing process of propylene-based block copolymer.
Embodiment 3a, embodiment 4a, embodiment 5a by add small amount of ethylene-alpha-olefin copolymer in propylene-based block copolymer C2-2a, can keep the transparency, the resistance to blocking equal with Embodiment C 2-2a, and impact strength significantly improve.By in propylene resin composition for packaging material of the present invention, adding ethene-alpha-olefin copolymer, can require Properties Control film rerum natura as can be known according to goods.
Influence the example of film rerum natura as propylene-ethylene copolymer (B), in the comparison of following expression embodiment 8a and comparative example 4a.In embodiment 8a, use the propylene-ethylene copolymer B-1a that makes by the metallocene catalyst class, the film rerum natura of the propylene resin composition for packaging material that obtains, the transparency, impact strength, shock-resistance excellence.On the other hand, in comparative example 4a, use the propylene-ethylene copolymer B-2a that is made by ziegler-natta catalyzer class, the molecular weight distribution (Mw/Mn) of this propylene-ethylene copolymer B-2a is wide, D SolMeasure also less, form distribution extensively.Therefore, the film of the propylene resin composition for packaging material that in comparative example 4a, obtains, the rigidity of film reduces, and is not suitable for film purposes such as high temperature steaming.
(the manufacturing of C2-1b) of [Production Example 1b] propylene-based block copolymer
(1) manufacturing of solid catalyst carrier
The SiO of sampling 300g in the distilling flask of 1L 2, add 800mL toluene, carry out slurryization, move the 4 mouthful flasks of liquid then to 5L, add 260mL toluene.Add the toluene solution (10wt% solution) of 2830mL methylaluminoxane (following is MAO), at room temperature stirred 30 minutes.Be warmed up to 110 ℃ with 1 hour, reacted 4 hours.Reaction cools to room temperature after finishing.After the cooling, removing supernatant toluene liquid, add toluene again and replace, is 95% until rate of displacement.
(2) manufacturing of solid catalyst (the metal catalyst composition is held to carrying of carrier)
In glove box, in 4 mouthfuls of flasks of 5L, take by weighing 2.0g [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride.Flask is moved to the outside, under nitrogen, add 0.46 liter of toluene and 1.4 liters of modulated M AO/SiO in (1) 2/ toluene slurry stirs to carry in 30 minutes and holds.Obtain [3-(1 ', 1 ', 4 ', 4 ', 7 ', 7 ', 10 ', 10 '-prestox octahydro dibenzo [b, h] fluorenyl) (1,1, the 3-trimethylammonium-5-tertiary butyl-1,2,3,3a-tetrahydrochysene pentalene)] zirconium dichloride/MAO/SiO 2/ toluene slurry carries out 99% displacement with normal heptane, and making final amount of slurry is 4.5 liters.This operates in room temperature and carries out.
(3) manufacturing of prepolymerization catalyst
In the autoclave of the band stirrer of internal volume 200L, import 404g synthetic solid catalyst component, 218mL triethyl aluminum, 100L heptane in above-mentioned (2), temperature is at 15～20 ℃ in keeping, after importing 1212g ethene, made it reaction in 180 minutes while stir.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 6g/L with solid catalyst component concentration.This prepolymerization catalyst, every 1g solid catalyst component contains the 3g polyethylene.
(4) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 5.8g/ and hour supply with the catalyst pulp of in above-mentioned (3), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.07mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.18 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.8MPa/G.
With the propylene-based block copolymer that obtains (C2-1b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-2b) of [Production Example 2b] propylene-based block copolymer
The solid catalyst carrier that use is made in Production Example 1b (1) is undertaken by following method.
(1) manufacturing of solid catalyst (the metal catalyst composition is held to carrying of carrier)
In glove box, in 4 mouthfuls of flasks of 5L, take by weighing phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (2, the 7-tertiary butyl fluorenyl) zirconium dichloride of 2.0g.Flask is moved to the outside, under nitrogen, add 0.46 liter of toluene and 1.4 liters of modulated M AO/SiO in (1) 2/ toluene slurry stirs to carry in 30 minutes and holds.The phenylbenzene methylene radical that obtains (the 3-tertiary butyl-5-methyl-cyclopentadienyl) (2,7-tertiary butyl fluorenyl) zirconium dichloride/MAO/SiO 2/ toluene slurry carries out 99% displacement with normal heptane, and making final amount of slurry is 4.5 liters.This operates in room temperature and carries out.
(2) manufacturing of prepolymerization catalyst
In the autoclave of the band stirrer of internal volume 200L, import 404g synthetic solid catalyst component, 218mL triethyl aluminum, 100L heptane in above-mentioned (1), temperature is at 15～20 ℃ in keeping, after importing 606g ethene, made it reaction in 180 minutes while stir.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 6g/L with solid catalyst component concentration.This prepolymerization catalyst, every 1g solid catalyst component contains the 3g polyethylene.
(3) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 10.9g/ and hour supply with the catalyst pulp of in above-mentioned (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.02mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.19 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.9MPa/G.
With the propylene-based block copolymer that obtains (C2-2b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-3b) of [Production Example 3b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 3b and make propylene-based block copolymer (C2-3b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 10.9g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.02mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.19 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.1MPa/G.
With the propylene-based block copolymer that obtains (C2-3b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-4b) of [Production Example 4b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 2b and make propylene-based block copolymer (C2-4b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 10.9g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.02mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.19 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.6MPa/G.
With the propylene-based block copolymer that obtains (C2-4b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-5b) of [Production Example 5b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 2b and make propylene-based block copolymer (C2-5b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 7.0g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.08mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.19 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.8MPa/G.
With the propylene-based block copolymer that obtains (C2-5b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-6b) of [Production Example 6b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 2b and make propylene-based block copolymer (C2-6b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 10.9g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.02mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.09 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.0MPa/G.
With the propylene-based block copolymer that obtains (C2-6b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-7b) of [Production Example 7b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 2b and make propylene-based block copolymer (C2-7b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 11.0g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.02mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.50 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.7MPa/G.
With the propylene-based block copolymer that obtains (C2-7b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-8b) of [Production Example 8b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 2b and make propylene-based block copolymer (C2-8b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 11.0g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.02mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with propylene, ethene, hydrogen continuously, making the gas composition in the gas phase polymerization apparatus is ethene/(ethene+propylene)=0.19 (mol ratio), hydrogen/ethene=0.001 (mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.7MPa/G.
With the propylene-based block copolymer that obtains (C2-8b) 80 ℃ of vacuum-dryings.
(the manufacturing of A-1b) of [Production Example 9b] acronal
Except with the following variation of polymerization process, use with the same method of Production Example 1b and make acronal (A-1b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 5.8g/ and hour supply with the catalyst pulp of in (3), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.07mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
After the slurry gasification that obtains, carry out gas solid separation, obtain propene polymer.With the acronal that obtains (A-1b) 80 ℃ of vacuum-dryings.
[Production Example 10b] acronal (I '-1b) manufacturing
(1) modulation of solid titanium catalyst component
952g Magnesium Chloride Anhydrous, 4420ml decane and 3906g 2-Ethylhexyl Alcohol 130 ℃ of heating 2 hours, are obtained homogeneous solution.In this solution, add the 213g Tetra hydro Phthalic anhydride, mixed 1 hour at 130 ℃ again, make the Tetra hydro Phthalic anhydride dissolving.
The homogeneous solution that obtains of operation like this is cooled to 23 ℃, remained on this homogeneous solution of dropping 750ml in-20 ℃ the titanium tetrachloride then with 1 hour at 2000ml.After the dropping, be warmed up to 110 ℃, when arriving 110 ℃, add 52.2g diisobutyl phthalate (DIBP), kept this temperature in 2 hours while after this stir with 4 hours temperature with the mixed solution that obtains.Then, filter when hot and gather solid part, make this solid part outstanding more turbid in the 2750ml titanium tetrachloride, and then 110 ℃ of heating 2 hours.
Heating is gathered solid part with heat filtering after finishing once more, uses 110 ℃ decane and hexane to clean, and can't detect titanium compound in scavenging solution.
Above-mentioned synthetic solid titanium catalyst component is preserved with the hexane slurry, dry its part, and the research catalyzer is formed.Solid titanium catalyst component contains the titanium of 2 weight %, the chlorine of 57 weight %, the magnesium of 21 weight % and the DIBP of 20 weight %.
(2) manufacturing of prepolymerization catalyst
In the autoclave of the band stirrer of internal volume 200L, import 56g transition metal catalyst component, 20.7mL triethyl aluminum, 7.0mL2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 80L heptane, temperature is at 5 ℃ in keeping, after importing the 560g propylene, made it reaction in 60 minutes while stir.Polymerization makes the solids component sedimentation after finishing, and removes supernatant liquor, uses washed with heptane 2 times.Make that the prepolymerization catalyst that obtains is outstanding more turbidly to be adjusted with heptane in refining heptane, make to be expressed as 0.7g/L with transition metal catalyst component concentration.This prepolymerization catalyst, every 1g transition metal catalyst component contains the 10g polypropylene.
(3) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 0.33g/ and hour supply with catalyst pulp as solid catalyst component, 3.8ml/ and hour supply with triethyl aluminum, 1.3ml/ and hour supply with dicyclopentyl dimethoxyl silane, carry out polymerization with the full liquid status that does not have gas phase to supply with propylene, 9NL/ in 30kg/ hour.The temperature of tubular reactor is that 70 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.4mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
After the gasification of the slurry that obtains, carry out gas solid separation, obtain acronal (I '-1b).With the acronal that obtains (I '-1b) 80 ℃ of vacuum-dryings.
[Production Example 11b] acronal (I '-2b) manufacturing
Except with the following variation of polymerization process, use with the same method of Production Example 1b make acronal (I '-2b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 4.8g/ and hour supply with the catalyst pulp of in (3), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.2MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply with hydrogen and make that the hydrogen concentration of gas phase portion is 0.07mol%, supply with ethene and make that the ethylene concentration of gas phase portion is 1.8mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.1MPa/G.
After the gasification of the slurry that obtains, carry out gas solid separation, obtain acronal (I '-2b).With the acronal that obtains (I '-2b) 80 ℃ of vacuum-dryings.
(the manufacturing of B-1b) of [Production Example 12b] propylene-ethylene copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 2b and make propylene-ethylene copolymer (B-1b).
(1) main polymerization
Fully replace and be to add the 9kg liquid propene in 10 ℃ the SUS system autoclave of internal volume 30L at nitrogen, add the ethene of 0.7MPa as dividing potential drop.Fully stir on one side on one side and be warmed up to 45 ℃, import with tube from catalyzer, pressurizeing in autoclave with nitrogen imports the mixing solutions of 0.6g solid catalyst component/300ml heptane and 0.5ml triethyl aluminum.Carry out polymerization in 20 minutes at 60 ℃, add methyl alcohol then, stop polymerization.After polymerization finishes, remove propylene, fully carry out nitrogen replacement, and separation of propylene-ethylene copolymer (B-1b).With propylene-ethylene copolymer of obtaining (B-1b) 80 ℃ of vacuum-dryings.
(the manufacturing of B-2b) of [Production Example 13b] propylene-ethylene copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 10b and make propylene-ethylene copolymer (B-2b).
(1) main polymerization
In the SUS of the abundant metathetical internal volume of nitrogen 30L system autoclave, add the 9kg liquid propene, fully stir on one side and be warmed up to 45 ℃ on one side.Dividing potential drop adds the ethene of 0.25MPa, the hydrogen of 42NL.Import with tube from catalyzer, pressurizeing in autoclave with nitrogen imports the mixing solutions of 0.05g solid catalyst component/200ml heptane and 0.5ml triethyl aluminum and 0.05ml dicyclopentyl dimethoxyl silane.Carry out polymerization in 15 minutes at 50 ℃, add methyl alcohol then, stop polymerization.After polymerization finishes, remove propylene, fully carry out nitrogen replacement, and separation of propylene-ethylene copolymer (B-2b).With propylene-ethylene copolymer of obtaining (B-2b) 80 ℃ of vacuum-dryings.
These results of expression in table 3 and table 4.
Figure A200780029515D00551
Figure A200780029515D00561
[embodiment 1b]
With respect to the propylene-based block copolymer of in Production Example 1b, making of 100 weight parts (C2-1b), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Cibaspecialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 antiblocking agent Sylophobic 505 (the AB agent 1 of weight part, particle diameter 3.9 μ m) (silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 5.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[embodiment 2b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-2b), in addition, carry out equally of 100 weight parts in Production Example 2b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b.The rerum natura of the film that expression obtains in table 5.
[embodiment 3b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-2b) of 100 weight parts in Production Example 2b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b, and the addition of antiblocking agent Sylophobic 505 (AB agent 1) become 0.3 weight part from 0.5 weight part, in addition, carry out equally.The rerum natura of the film that expression obtains in table 5.
[embodiment 4b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-2b) of 100 weight parts in Production Example 2b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b, and antiblocking agent is become the Sylophobic 704 (AB agent 2, particle diameter 6.2 μ m) (silysia KCC of Fuji) of 0.5 weight part from the Sylophobic 505 (AB agent 1) of 0.5 weight part, in addition, carry out equally.The rerum natura of the film that expression obtains in table 5.
[embodiment 5b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-2b) of 100 weight parts in Production Example 2b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b, and the addition of antiblocking agent Sylophobic 505 (AB agent 1) become 0 weight part (adding) from 0.5 weight part, in addition, carry out equally.The rerum natura of the film that expression obtains in table 5.
[embodiment 6b]
With respect to the propylene-based block copolymer of in Production Example 3b, making of the combination 80 weight parts (acronal of in Production Example 9b, making of C2-3b) and 20 weight parts (100 weight parts of A-1b), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (silysia KCC of Fuji) (AB agent 1), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 5.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[embodiment 7b]
Acronal among the replacement embodiment 6b (A-1b), the acronal that use is made in Production Example 10b (I '-1b), in addition, carry out equally.The rerum natura of the film that expression obtains in table 5.
[embodiment 8b]
The propylene-based block copolymer of in Production Example 4b, making (the straight chain shape new LDPE (film grade) (EVOLUE SP1510 (density=0.915g/cm of C2-4b) and 10 weight parts with respect to combination 90 weight parts 3The prime polymer of Co., Ltd. trade mark) 100 weight parts of (ethene-alpha-olefin copolymer (D-1)), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 5.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[embodiment 9b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-5b), in addition, carry out equally of 100 weight parts in Production Example 5b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b.The rerum natura of the film that expression obtains in table 5.
[embodiment 10b]
With respect to the propylene copolymers of in Production Example 9b, making of the combination 80 weight parts (propylene-ethylene copolymer of in Production Example 12b, making of A-1b) and 20 weight parts (100 weight parts of B-1b), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (silysia KCC of Fuji) (AB agent 1), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 5.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
Figure A200780029515D00611
[comparative example 1b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-6b), in addition, carry out equally of 100 weight parts in Production Example 6b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b.The rerum natura of the film that expression obtains in table 6.
[comparative example 2b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-7b), in addition, carry out equally of 100 weight parts in Production Example 7b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b.The rerum natura of the film that expression obtains in table 6.
[comparative example 3b]
(C2-1b) replaces with the propylene-based block copolymer of the making (C2-8b), in addition, carry out equally of 100 weight parts in Production Example 8b with the propylene-based block copolymer of 100 weight parts among the embodiment 1b.The rerum natura of the film that expression obtains in table 6.
[comparative example 4b]
With respect to the acronal of in Production Example 10b, making of combination 80 weight parts (I '-1b) and the propylene-ethylene copolymer of in Production Example 13b, making of 20 weight parts (100 weight parts of B-2b), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (silysia KCC of Fuji) (AB agent 1), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 6.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
[comparative example 5b]
With respect to the acronal of in Production Example 11b, making of combination 80 weight parts (I '-2b) and the propylene-ethylene copolymer of in Production Example 12b, making of 20 weight parts (100 weight parts of B-1b), utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 6.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 4.5m/min
Thickness: 70 μ m
In table 7, gathered D SolThe influence that group pair of films rerum natura is brought.In embodiment 2b, the balance excellence of rigidity, shock-resistance, the transparency is suitable for transparent boiling film, protective membrane purposes as can be known.On the other hand, in comparative example 1b, though the transparency is excellent, poor impact resistance is so be not suitable as the boiling film.In addition, in comparative example 2b, though rigidity, shock-resistance are good, the transparency is poor, so be not suitable for transparent boiling film and protective membrane.In addition, D among the comparative example 3b Sol[η] low, so shock-resistance reduces, be not suitable as the boiling film.As can be known from these results, Propenes resin composition of the present invention is suitable for transparent boiling film and protective membrane.
[table 6]
Figure A200780029515D00641
[table 7]
Figure A200780029515D00651
Gathered the film physical data and at the Young's modulus of high temperature (135 ℃) at table 8.In comparative example 5b, the fusing point of PP part is low to be 138 ℃, so near the Young's modulus 135 ℃ significantly reduces, can not the withstand high temperatures boiling handle (135 ℃ of temperature).On the other hand, in embodiment 1b, embodiment 2b, embodiment 6b, embodiment 7b, increase to more than 2 times at 135 ℃ Young's modulus.Particularly in embodiment 1b, fusing point also becomes the highest up to 156 ℃ at 135 ℃ Young's modulus.In addition, among embodiment 6b, the embodiment 7b, be purpose with the thermotolerance of improving propylene-based block copolymer of the present invention, the dystectic acronal of fusion.In embodiment 6b, embodiment 7b, 135 ℃ Young's modulus improves nearly 4 times with respect to comparative example 5b, and fully the withstand high temperatures boiling is handled.
Figure A200780029515D00661
In table 9, gathered film rerum natura comparison by the difference generation of manufacture method.Embodiment 1b makes propylene-based block copolymer (C2-1b) with 2 stages polymerizations in the presence of metallocene catalyst (M1).The acronal that embodiment 10b will make in the presence of metallocene catalyst (M1) ((make and the propylene-based block copolymer (composition that C2-1b) is same for A-1b) and propylene-ethylene copolymer of making in the presence of metallocene catalyst (M2) by the melting mixing of B-1b).Both film rerum naturas have same physics values such as rigidity, shock-resistance, HAZE.No matter the manufacture method of Propenes resin composition 2 stage polymerization of the present invention that hence one can see that, melting mixing as long as enter compositing range of the present invention, just can be suitable for wrapping material such as transparent boiling, protective membrane.
In addition, comparative example 4b is in the presence of ZN catalyzer class, makes acronal and propylene-ethylene copolymer respectively, and make its melting mixing and Propenes resin composition.With respect to embodiment, the rigidity of comparative example 4b, shock-resistance are all low, are not suitable for boiling.
[table 9]
In table 10, be illustrated in the result of study of the antiblocking agent that adds in the Propenes resin composition of the present invention.Embodiment 2b, embodiment 3b add antiblocking agent AB-1 (particle diameter 3.9 μ m) 0.5PHR, 0.3PHR respectively, and embodiment 4b adds antiblocking agent AB-2 (particle diameter 6.2 μ m) 0.3PHR's.In addition, embodiment 5b is the system of not adding antiblocking agent fully.
[table 10]
Figure A200780029515D00681
By embodiment 2b, 3b, 5b as can be known, if increase the addition of antiblocking agent, resistance to blocking will improve.In addition, by the comparison of embodiment 3b and embodiment 4b, the side that the particle diameter of antiblocking agent is big has equal high transparent, but that resistance to blocking improves effect is big.On the other hand, because embodiment 5b does not add antiblocking agent,, be unsuitable for the high temperature steaming purposes so resistance to blocking is poor.But the binding property height of the film of embodiment 5b is so can be applied to self-adhesion mould assembly protective membrane.
(the manufacturing of C2-9b) of [Production Example 14b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 1b and make propylene-based block copolymer (C2-9b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 2.3g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.17mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.26 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.9MPa/G.
With the propylene-based block copolymer that obtains (C2-9b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-10b) of [Production Example 15b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 1b and make propylene-based block copolymer (C2-10b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 2.3g/ and hour supply with the catalyst pulp of in (2), making, 2.5ml/ hour supply triethyl aluminum, carry out polymerization with the full liquid status that does not have gas phase as solid catalyst component to supply with propylene, 2NL/ in 30kg/ hour.The temperature of tubular reactor is that 30 ℃, pressure are 3.1MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 0.17mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.0MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with continuously propylene, ethene, hydrogen, make gas composition in the gas phase polymerization apparatus be ethene/(ethene+propylene)=0.09 (mol ratio),
Figure A200780029515D0031171357QIETU
(mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 1.1MPa/G.
With the propylene-based block copolymer that obtains (C2-10b) 80 ℃ of vacuum-dryings.
(the manufacturing of C2-11b) of [Production Example 16b] propylene-based block copolymer
Except with the following variation of polymerization process, use with the same method of Production Example 10b and make propylene-based block copolymer (C2-11b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 0.27g/ and hour supply with catalyst pulp as solid catalyst component, 3.1ml/ and hour supply with triethyl aluminum, 1.0ml/ and hour supply with dicyclopentyl dimethoxyl silane, carry out polymerization with the full liquid status that does not have gas phase to supply with propylene, 51NL/ in 30kg/ hour.The temperature of tubular reactor is that 70 ℃, pressure are 3.2MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 3.1mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.1MPa/G.
The slurry that obtains is transferred to the transfer pipet of internal volume 2.4L, makes this slurry gasification, carry out gas solid separation, then the homopolymer polypropylene powder is sent in the gas phase polymerization apparatus of internal volume 480L, carry out the ethylene/propene block copolymerization.Supply with propylene, ethene, hydrogen continuously, making the gas composition in the gas phase polymerization apparatus is ethene/(ethene+propylene)=0.32 (mol ratio), hydrogen/ethene=0.3 (mol ratio).Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 0.5MPa/G.
With the propylene-based block copolymer that obtains (C2-11b) 80 ℃ of vacuum-dryings.
[Production Example 17b] acronal (I '-3b) manufacturing
Except with the following variation of polymerization process, use with the same method of Production Example 10b make acronal (I '-3b).
(1) main polymerization
Continuously in the with well circulating tubulose polymerizer of internal volume 58L, hour supply with hydrogen, 0.27g/ and hour supply with catalyst pulp as solid catalyst component, 3.1ml/ and hour supply with triethyl aluminum, 1.0ml/ and hour supply with dicyclopentyl dimethoxyl silane, carry out polymerization with the full liquid status that does not have gas phase to supply with propylene, 51NL/ in 30kg/ hour.The temperature of tubular reactor is that 70 ℃, pressure are 3.2MPa/G.
The slurry that obtains is sent to the container polymerizer of the band stirrer of internal volume 100L, carries out polymerization again.Supplied with propylene to polymerizer with 15kg/ hour, and supply hydrogen makes that the hydrogen concentration of gas phase portion is 3.1mol%.Carry out polymerization with 70 ℃ of polymerization temperatures, pressure 3.1MPa/G.
After the slurry gasification that obtains, carry out gas solid separation, obtain propene polymer.With the acronal that obtains (I '-3b) 80 ℃ of vacuum-dryings.
These results of expression in table 11.
[table 11]
Figure A200780029515D00711
Produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 7.5m/min
Thickness: 30 μ m
[comparative example 6b]
(C2-9b) replaces with the propylene-based block copolymer of the making (C2-10b), in addition, carry out equally of 100 weight parts in Production Example 15b with the propylene-based block copolymer of 100 weight parts among the embodiment 11b.The rerum natura of the film that expression obtains in table 12.
[comparative example 7b]
(C2-9b) replaces with the propylene-based block copolymer of the making (C2-11b), in addition, carry out equally of 100 weight parts in Production Example 16b with the propylene-based block copolymer of 100 weight parts among the embodiment 11b.The rerum natura of the film that expression obtains in table 12.
[comparative example 8b]
With respect to the acronal of in Production Example 11b, making of combination 75 weight parts (I '-3b) and the ethene-octene copolymer of 25 weight parts (D-2b) (Engage8842 (registered trademark): dupon dow elastomer Co., Ltd. produces, density=0.858 (g/cm 3)) 100 weight parts, utilize rotary drum to mix the thermo-stabilizer IRGANOX1010 (Ciba specialty chemicals Co., Ltd.) of 0.1 weight part, 0.1 the thermo-stabilizer IRGAFOS168 of weight part (Ciba specialty chemicals Co., Ltd.), 0.1 the calcium stearate of weight part, 0.5 the antiblocking agent Sylophobic 505 of weight part (silysia KCC of Fuji), carry out melting mixing with twin screw extruder then, the polypropylene-based resin composition of modulation partical, with T mould forcing machine [specifications and models GT-25A, plastics engineering institute of Co., Ltd. produces], make casting films.The rerum natura of expression film in table 12.
＜melting mixing condition 〉
Parallel dual-screw mixing roll: specifications and models NR2-36, Nakatani Kikai Co., Ltd. produce
Melting temperature: 240 ℃
Screw speed: 200rpm
Feeder rotating speed: 400rpm
＜film moulding 〉
25mm Φ T mould forcing machine: specifications and models GT-25A, plastics engineering institute of Co., Ltd. produce
Extrusion temperature: 230 ℃
Chill-roll temperature: 30 ℃
Accept speed: about 7.5m/min
Thickness: 30 μ m
[table 12]
Figure A200780029515D00731
The gas-premeable and the mechanical characteristics that in table 12, have gathered film.The film of embodiment 11b is high gas-premeable and is high rigidity as can be known, is suitable as preservative film.On the other hand, in comparative example 6b, D SolIn the ethene ratio of components scope of the invention in low, gas-premeable descends.In addition, comparative example 7b is the film that is made of ZN catalyzer based block copolymer, compares with embodiment 11b, and the rigidity of film is low.In addition, though comparative example 8b has gas-premeable and the rigidity same with embodiment 11b, because comprise the operation of cooperation, melting mixing acronal and ethene-octene copolymer, so there is big etc. the problem of manufacturing cost height or energy expenditure.
Utilizability on the industry
Propenes resin composition or propylene copolymers structure by satisfying special properties of the present invention The film and the sheet material that become, its high transparent, rigidity, low temperature resistance to impact, resistance to blocking and bonding The property control excellence, so be suitable for boiling with film, diaphragm, medical container, preservative film and Their sheet material.

Claims (15)

1. propylene resin composition for packaging material is characterized in that:
Comprise the acronal (A) of the following important document of satisfying of 60～90 weight % (a1)～(a2) and propylene one ethylene copolymer (B) that satisfies following important document (b1)～(b4) of 40～10 weight %, wherein, (A)+(B)=100 weight %,
Acronal (A):
(a1) melt flow rate (MFR) (MFR, ASTM D1238,230 ℃, load 2.16kg) is 0.1～40 (g/10min),
(a2) fusing point of measuring with differential scanning type calorimeter (DSC) (Tm) is 145 ℃～170 ℃,
Propylene-ethylene copolymer (B):
(b1) content from the structural unit of ethene is more than the 15mol% and less than 45mol%,
(b2) be 1.8dl/g～3.5dl/g in naphthane solvent, 135 ℃ limiting viscosity [η],
(b3) molecular weight distribution (Mw/Mn) is below 3.5,
(b4) be more than the 95 weight % 23 ℃ of parts that dissolve in n-decane.
2. propylene resin composition for packaging material as claimed in claim 1 is characterized in that:
The molecular weight distribution (Mw/Mn) of described acronal (A) is below 3.5.
3. propylene resin composition for packaging material as claimed in claim 1 or 2 is characterized in that:
Described propylene-ethylene copolymer (B) polymerization and obtaining in the presence of metallocene catalyst.
4. as each described propylene resin composition for packaging material in the claim 1～3, it is characterized in that:
(a1) melt flow rate (MFR) of described acronal (A) is 0.1～10g/10min, and (b1) of described propylene-ethylene copolymer (B) is 15mol%～25mol% from the content of the structural unit of ethene.
5. as each described propylene resin composition for packaging material in the claim 1～3, it is characterized in that:
(b1) of described propylene-ethylene copolymer (B) from the content of the structural unit of ethene greater than 25mol% and less than 45mol%.
6. propylene resin composition for packaging material is characterized in that:
Comprise the following important document of satisfying of 60～90 weight % (a1 ')～(a2 ') at 23 ℃ of part (D that are insoluble to n-decane Insol) and 40～10 weight % satisfy following important document (b1 ')～(b3 ') at 23 ℃ of part (D that dissolve in n-decane Sol), and melt flow rate (MFR) (MFR, ASTM D1238,230 ℃, load 2.16kg) is in the scope of 0.1～20g/10min,
Be insoluble to the part (D of n-decane Insol):
(a1 ') is below the 2 weight % from the content of the structural unit of ethene,
The fusing point (Tm) that (a2 ') measures with differential scanning type calorimeter (DSC) is 145 ℃～170 ℃,
Dissolve in the part (D of n-decane Sol):
(b1 ') is more than the 15mol% and less than 45mol% from the content of the structural unit of ethene,
(b2 ') is 1.8dl/g～3.5dl/g in naphthane solvent, 135 ℃ limiting viscosity [η],
(b3 ') molecular weight distribution (Mw/Mn) is below 3.5.
7. propylene resin composition for packaging material as claimed in claim 6 is characterized in that:
Described Propenes resin composition is in the presence of metallocene catalyst, the continuous propylene-based block copolymer of implementing [operation 1] and [operation 2] and obtaining, wherein,
[operation 1] makes propylene and vinyl polymerization as required, is manufactured on 23 ℃ of part (D that dissolve in n-decane Sol) be the operation of the following polymkeric substance of 0.5 weight %,
[operation 2] makes propylene and ethylene copolymer, is manufactured on 23 ℃ of part (D that are insoluble to n-decane Insol) be the operation of the following multipolymer of 5.0 weight %.
8. as claim 6 or 7 described propylene resin composition for packaging material, it is characterized in that:
Described part (the D that dissolves in n-decane Sol) (b1 ') be 15mol%～25mol% from the content of the structural unit of ethene.
9. propylene resin composition for packaging material as claimed in claim 8 is characterized in that:
Comprise that also the content from the structural unit of ethene is ethene-propylene copolymer (B ') of 25～85mol%.
10. as claim 6 or 7 described propylene resin composition for packaging material, it is characterized in that:
Described part (the D that dissolves in n-decane Sol) (b1 ') from the content of the structural unit of ethene greater than 25mol% and less than 45mol%.
11., it is characterized in that as each described propylene resin composition for packaging material in the claim 1～10:
Comprise that also density is 0.850～0.920g/cm 3Ethene-alpha-olefin copolymer (D).
The boiling that obtains 12. make each described propylene resin composition for packaging material moulding in the claim 1～11 is with film or sheet material.
The protection that obtains 13. make each described propylene resin composition for packaging material moulding in the claim 1～11 is with film or sheet material.
The medical container film for packaging or the sheet material that obtain 14. make each described propylene resin composition for packaging material moulding in the claim 1～11.
The Freshkeeping Packaging that obtains 15. make each described propylene resin composition for packaging material moulding in the claim 1～11 is with sheet material or film.
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